Prepared resin



Dec. 1, 1936.

C. A. THOMAS ET AL PREPARED RESIN Filed June 17, 1 930 Patented Dec. 1, 1936 PATENT 'oFF c PREPARED RESIN Charles A. Thomas and William H. Carm'ody, Dayton, Ohio, assignors, by mes'ne assignments, to Monsanto Petroleum Chemicals, Inc., Day-- ton, Ohio, a corporation of Delaware Application June 17, 1930,'Serial No. 461,798

16 Claims.

This invention relatesto the manufacture of' artificial or prepared resins. I

One of the principal objects of this invention is to provide such a prepared resin which has characteristics markedly superior in certain respects to the natural resins."

Another object of the invention is to provide a method of producing a prepared resin of controlled character, good color and hardness.

Still another object of the invention is to pro-. vide apparatus for carrying out the above method and for producing the above product.

Other objects and advantages of the invention will be apparent from the following description when taken in connection with the accompanying drawing and appended claims.

The single view of the drawing is a diagrammatic representation of apparatus for practicing the method, and for producing the resin-like material of the present invention.

Reference'is herein made to the co-pending application of Charles A. Thomas and Carroll A. Hochwalt, Serial No. 294,491,'now Patent No. 1,836,629, filed July 21, 1928, and to the co-pend ing applications of Carroll A. Hochwalt, Serial No. 461,799, new Patent No. 2,035,233, fil'ed of even date herewith, and of CharlesA. Thomas, Serial No. 461,807, filed of even date herewith, which relate to the production of resins of a similarn character;

In the practicing of this inventiomunsaturated hydrocarbon compounds are caused to react in the presence of a suitable catalyst or'actiyating agent, such as anhydrous aluminum chloride, to,"

produce by polymerization an amorphous resinous reaction product, which is found to'ciintafin an unsaturated hydrocarbon. compound or com-- pounds of high molecular weight. It hasbeen found that this hydrocarbon resin has a molecular weight of about 900'to 1400,'and it is believed to have the empirical formula (CllHlll-Z) x. By subjecting this material to a saturating treatment, such as a hydrcgenating-treatment, so that plural bonds of the unsaturated resinous reaction prodnot are more or less completely saturated, an improved resin of=lighter color and increased'hardness is obtained. V i

Unsaturated hydrocarbon -compounds from various sources may be used in carrying out this invention. Thus cracked distillate, or special fractions of the cracked distillate such as that .55 pure unsaturated hydrocarbon compounds, which olefine with a diolefine under such controlled conditions. For example, diolefine compounds such as hexadiene, isoprene and butadiene react with 'olefine compounds such as the amylenes (including symmetrical methyl ethyl ethylene, unsymmetrical methyl ethyl ethylene, tri-methyl eth ylene, and normal propyl ethylene) ethylene, propylene, octylene, and the like, in the above manner. These compounds are mentioned as representative members of their particular groups which will react with good results to produce a resin reaction product resembling in properties the natural resins.

4 a As an example of the carrying of this invention into effect, the following procedure is described for the reaction or polymerization of normal propyl ethylene with hexadiene. A mixture of these unsaturated hydrocarbons, in the proportion of about one to two. mols of normal propyl ethylene to about one mol. of hexadiene, is placed within a container or polymerizing vessel. I 0 which is in turn enclosed within a suitable jacket I I hav- 4 ing valve controlled inlet and outlet connections I2 and 13 for thelsupplying of water to jacket H for controlling the temperature of the mass within thelcontainer. A cover I5 is fastened in gas tight manner on the upper end of the vessel, and

L this cover is provided with a filling 'opening'non mally closed by a plug l6 through which material may be supplied to the interior. Cover 15- supports a motor n, mounted in any suitable fashibn, the shaft iii of which projects downwardly into the vessel and carries a suitable stirrer or agitator '19 at its lower-end. Leading off from the top of chamber III is a reflux condenser coil 20 positioned within a suitable cooling jacket 2| to whichcool- The unsaturated hydrocarbon compounds are 55 fed into the container Ill through a pipe controlled by valve 26 leading from a suitable source of Supply. The activating compound, such as,

contents of the-container I 0 are being agitated by the motor driven stirrer l9. For example, presuming that twenty-five gallons of a mixture of normal propyl ethylene and hexadiene are to be treated within container l0, aluminum chloride may be satisfactorily added in quantities of approximately six to eight ounces at a time. With the addition of the first batch of aluminum chloride, there is a rather active chemical reaction or condensation with a resultant rise in temperature. It is desirable to control the temperature of the reaction inasmuch as this has'a bearing upon the character of the resultant resin, particularly the hardness thereof. The reaction is preferably carried out above 20 C., as then the of catalyst for 100 c. c. of unsaturated hydrocar-' resultant resin is very materially harder and the yield increases somewhat. However, it is desirable where an atmospheric polymerizing vessel is used that the temperature should not be permitted to-rise much above 40 C. Otherwise the polymerizing vessel should be kept under pressure to prevent undue volatilization and loss of resin. Moreover, polymerization at higher temperatures, such as above 65 0., generally gives a,

resin of poorer color. Very satisfactory results are secured when the temperature is controlled between 25 and 35 0., this being readily accomplished by introducing the aluminum chloride in small amounts with proper agitation to prevent local overheating and bysupplying cooling liquid to the cooling jacket II. This polymerizing reaction is carried out in the absence of water.

Additional batches of aluminum chloride are added from time to time as may be done without unduly increasing the temperature within con tainer l0, and this is repeated with continuous agitation until no further temperature rise results. The amount of aluminum chloride used is also controlled in accordance with the materials being treated, as this is found to have a bearing upon the yield. It is found that the larger the volume of active ingredients being treated at any one time, the less the amount of v catalyst needed for optimum results. Thus when treating the above mixture in twenty-five gallon batches, very satisfactory results are secured by the addition of about three pounds of catalyst, this being equivalent to approximately 1.4 grams bons. Where smaller batches are being treated, such for example as a batch of 100 c. c., an increased proportion of catalyst is used to give maximum yield, generally about 3.5 to 3.7 grams of aluminum chloride per 100 c. c. of active ingredients giving optimum results. The quantity of catalyst needed for best results can be readily determined by tests for the particular ingredients and theparticular volume of the ingredients being treated, so that this amount can be used in regular, plant production. In any event, it is desirable that the amount of catalyst used be not increased materially over four grams per 100 c. c. of active ingredients, as the character of the resultant resin may be deleteriously influenced.

In addition to aluminum chloride, other compounds which hydrolyzein water gi i g an acid reaction will function satisfactorily to cause the conversion of the unsaturated hydrocarbons into resin,for example chlorides .of iron, boron, zinc, antimony, indium, titanium and tin; benzene sulfonicacid; propyl alcohol saturated with HCl as; ethyl sulfate, and aniline hydrobromide. The time of the treatment is also found to have a bearing upon the resultant resin, particularly the color. as twelve hours, but it is found desirable to not leave the catalyst in contact with the material for a. period of time much in excess of this, as the resin may be darkened. The reaction is preferably completed in less time, suchas about four to six hours, this giving optimum results. A thermometer 28 may be mounted in the cover 15 to conveniently indicate the temperature of the carries a motor 35 having a shaft 36 extending The reaction may proceed as much within the container and carrying at the lower end thereof suitable stirring blades 31. A valve controlled pipe 38 may be used to supply neutralizing liquid from a suitable reservoir (not shown). Various water soluble alkalies may be used for this neutralizing, but preferably ammonium hydroxide is employed as the excess of this material can subsequently be removed by distillation and it has no injurious effects upon the resulting resin.

The neutralizing treatment is also preferably carried out in the presence of a non-aqueous organic hydroxy compound which is effective to supply hydroxyl radicals for the decomposition and precipitation of the aluminum chloride or other activating agentpresent. An alcohol, such as ethyl alcohol, functions very satisfactorily for this purpose. Thus with the quantities specified above, about three gallons of a mixture of about 40% by volume of ammonium hydroxide (28% NI-Ia) and 60% by volume of ethyl alcohol gives good results. The stirrer 31 is then started, and the polymerized reaction massis introduced slowly from container I 0 in a controlled stream by pipe 30 into the agitated neutralizing agent within tank 32. The neutralization in the presence of an organic hydroxy compound of this character with proper agitation gives a granular precipitate of aluminum hydroxide which is readily removed by filtration. The neutralization could be carried out in the presence of water but this renders subsequent distillation more diflicult and is apt to result in quantities of water being' occluded in the resin at this time. Other organic hydroxy liquids which are miscible with water, such as methyl alcohol, acetone, etc., may be used for this purpose. An alcohol or other organic hydroxy liquid saturated with NHs gas can be used for. the neutralization with very satisfactory results. a

The neutralization is accompanied byta color change of the reacting mass, the polymerized product changing from a black' or dark red to a yellowish red color 'and thus indicating that the neutralization is completed and the mixture basic in character. The agitating and neutralizing action is generally completed in about half an hour.

The ammonia neutralizes all of the aluminum of aluminum hydroxide. Some of the ammonium chloride formed in the reaction also precipitates in the organic solvents, and a portion of the resin reaction product may also precipitate. In order .to insure that the resin is completely dissolved before filtration, an organic solvent which is immiscible in water, such as benzol, carbon -tetrachloride, ethylene dichloride, and the like, is added to the neutr g tank 32 prior to filtration- This organic so vent may be present during the neutralizing reaction and may'be'initially added poundremains undissolved and is carried down i in the precipitate. ,Tank 32 is provided with a temperature controlling jacket 42 having valve controlled inlet and. outlet connections 43 and 4d, respectively, by means of which a heating 'medium such as steam, or hot water may besupplied to the heating jacket. After the neutralizing reaction is completed, the contents of tank 32 are preferably heated with steam by jacket." to a temperature of about 60 C. to insure that the produced resinous product is all dissolved. During this heating reaction, substantially all the excess ammonia is liberatedand passes through the distillate offtake 45 having control valve 46.

The mass is then passed by discharge pipe 48 having control valve 49 ton suitable filter, such as afilter press 50, where the' undissolved mate rials are removed from the liquid. The filtered sludge removed in'filter press 50 is'preferably treated to recover aluminum oxide (A1203) and ammonium chloride asby-products. The filtrate passes by pip'e having control valve 52 into a hydrogenating vessel 53 provided with a tight fitting cover 54 carryinga motor 55. The motor is connected to 9. depending shaft 56 which extends down adjacent the lower portion of container 53 and is provided at its lower end'with a rotary dispersion member adapted to effect thorough agitation and to eifect intimate mix ture of the materials within the container 53. As

municating with a peripheral discharge.

bottom of the disk carries-a conical baflle forming.

shown; this member comprises a rotary disk '58 which is hollow, or has radial passages 59 com- The - an intake mouth 50 which communicates with a central passage 5|, the latter in turn communi cating with the passage or passages 59. Cover 54 carries a pipe 63 which extends down within the container and terminates in an upturned n'omle or jet 54 directed into the intake mouth 6|].

After the filtrate has been introduced into vessel 53, a small amount of a suitable-catalyst is then' introduced through the opening in cover 54 normally closed by a plug 56, Satisfactory re- ,sults are secured with a catalyst such as platinum admitted in a controlled stream through pipe 83 controlled'by valve 51. The hydrogen gas passes along with the liquid and suspended platinum black or other catalyst into the intake mouth 50 unsaturated hydrocarbons in of the rotary member, and is thrown outwardly by centrifugal force through the peripheral discharge of this member, thereby securing a highly efiective mixing and intimate contact of the hydrogen gas withthe dissolved resin reaction prod 5 not. In the presence of a highlyeifective catalyst of this character, the unsaturated resin reaction product takes up hydrogen to saturate plural bonds to thereby more or less-completely saturate this resin reaction product. The hydro: genating reaction may be carried out at ordinary temperatures, a suitable time being permitted for the reaction to go to the desired state of comple-' tion. For example, a reaction time of about three hours, gives very satisfactory results.

The high speed agitation is then stopped, valve 61 closed to terminate the introduction of hydrogen gas and the resultant hydrogenated material isthen passed by pipe 88 having control valve 58 to a suitable filter, such as a filter press I8, where the suspended catalyst is removed from the hydrogenated liquid and thereby recoifered, this catalyst being suitable for repeated. use in the process- The filtrate passesby' pipe 12 having control valve 13 to a concentration still 14 having an external heating jacket 15 provided with valve controlled inlet and outlet connections 15 and", respectively, forthe introductionof a suitable heating medium such as steam.

Vessel I4 is provided with a tight fitting cover carrying a distillate ofitake pipe I8 communieating witha suitable condenser (not shown)- Steam is admitted to jacket l5 to distill oilthe more volatile constituents, including the benzol and alcohol,.which pass off through the ofltake 78 and are condensed and may be recovered for repeated use in the process. Distillation is con-.' tinued until a thermometer in the distillation line rises to approximately 100 C. at which time substantially all of the alcohol and :benzol, and any '40 water, will have been driven'ofi of the resulting resin, which is left in the vessel Has a semifluid or pasty mass.

If 'desired, the concentration of the resin may; be controlled so as to leave a calculated amount of solvent in theresin so that it is maintained in solution form. This solution may then be withdrawn from the, concentrating still 14 through pipe 80 having ';control valve 8|, and through or other solvent suchas solventnaphtha, may be used directly inthepaint and varnish industries,

or for other suitable uses without concentratingto dryness. If a solid resin is desired, the distillation is continued as describedabove until substantially allof the readily volatile solvents have been driven off, suflicient solvent or retained higher oils being left in the resin so that it is suffici'ently fluid to flow through pipe to into an agitating and drying vessel 85.

:This is preferably aclosed vessel, having an ofi'take 85 leading to a suitable vent or stack, and

a surrounding jacket 81 having valve'controlled l inlet and outlet connections 88 and 89 re'spective- 1y for supplying 'a heating medium suchas steam blades or paddles 9|, each blade being provided with a plurality of perforations or relatively large holes '82. The shaft 9|! extends to ma exterior of the vessel and carries a sui'1b1e pulley 93, or is otherwise connected to a line shaft or driving motor, so that the stirrer may be rotated at a relatively slow speed. A fiuid is supplied to the container 85 by means of pipe 95 having control valve 86 communicating with a suitable perforated coil 91 mounted within the bottom of vessel 85 beneath the agitator 90. Preferably a non-aqueous non-oxidizing gaseous fluid, such as carbon dioxide, is thus introduced and passed through the resultant resinous mass while it is being agitated,

so that intimate contact of the treated gas with increase in the drying of the resin without injury to the resin. Thus heated oil, at a temperature of about 180 C. may be supplied to this external jacket, and the drying operation completed in several hours. This treatment drives off any remaining solvent and higher oils present in the resin which tend to make it soft. By the use of a non-oxidizing fiuid, a clear light colored resin of good character is regularly obtained. Air may be used, if desired, for the drying operation; but generally the temperature of the agitated mass should be lowered and the drying operation should be continued for a longer time to obtain a hard resin of good color. By avoiding the use of steam or substantial quantities of water throughout the process, the occlusion of water in the resin is avoided and a clear product obtained. The resin is then removed from the drying vessel 85, as by the bottom outlet 98, and placed in suitable collecting troughs or shallow pans where it is allowed to cool or harden. While any suitable form of feed from one vessel to the other may be provided, a gravity feed throughout the entire system, such as disclosed herein, is preferred for commercial installations.

While a particular treatment for the hydrogenation of the resin as obtained from a mixture of normal propyl ethylene and hexadiene has been specifically described above, it is to be understood that this method is generally applicable to the treatment of unsaturated hydrocarbon resin reaction products.

It is to be.understood that the term unsaturated hydrocarbons" as used herein, refers to hydrocarbon compounds which unite with other compounds, such for example, as the halogens, to form addition products without splitting off a new compound. Unsaturated hydrocarbons are capable of giving the Baeyer test for unsaturation. (Textbook of Organic Chemistry, Holle man, 6th ed. page 131.)

The hydrogenated resin so prepared in accordance with this invention is found to have a light yellow color, is generally clear, and is harder than the unsaturated hydrocarbon resin which has not been subjected to the hydrogenating treatment. When dissolved in a suitable oil solvent, such as naphtha, the resin forms a clear almost colorless liquid, which when brushed onto a surface leaves a clear film. The prepared resin is non-acid in reaction andis unsaponifiable. Another very important and desirable characteristic of the prepared resin is that it does not retard the oxidizing action of linseed oil, so that a varnish can be prepared with this resin which compares favorably in speed of drying with lacquers.

While the method herein described and the apparatus for carrying out .that method and the products so produced constitute preferred embodiments of our invention, it is to be understood that the invention is not limited to this precise method or apparatus, or precise product, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claims.

What is claimed is: I. In the manufacture of prepared resin, the method which comprises reacting an unsaturated hydrocarbon'having one double bond and an unsaturated hydrocarbon having more than one double bond in the presence of a metallic halide activating agent which hydrolyzes to give-an acid reaction to produce an unsaturated resinous reaction product, and then subjecting the resinous reaction product to the action of hydrogen.

2. In the manufacture of prepared resin, the method which comprises reacting an olefine with a diolefine in the presence of a metallic halide activating agent which hydrolyzes to give an acid reaction to produce a resinous reaction product, and then hydrogenating the formed resinous reaction product. a v

3. A prepared resin comprising a hydrogenated reaction product of a mixture of unsaturated hydrocarbons comprising essentially an oleflne and a diolefine reacted together.

4. In the manufacture of prepared resin, the method which comprises reacting together a mixture of unsaturated hydrocarbons of varying degrees of unsaturationincluding a diolefine in the presence of a metallic halide activating agent which hydrolyzes to give an acid reaction, to give a resinous reaction product, neutralizing the reaction product mass with an alkaline material in the presence of a hydroxy compound selected from the group consisting of methyl alcohol and ethyl alcohol, adding, prior to filtration, an organic solvent for the resinous reaction product, the solvent being immiscible with water, filtering the undissolved materials from the neutralized method which comprises. reacting together a mixture of unsaturated hydrocarbons including a,

diolefine in the presence of a metallic halide activating agent which hydrolyzes to give an acid reaction, to give a resinous reaction product, neutralizing the reaction product mass with an alkaline material, adding, prior to filtration, an organic solvent for the resinous reaction product, the solvent being immiscible with water, filtering the undissolved materials from the neutralized mass, passing a stream of hydrogen gas into the filtrate in the presence of a hydrogenation catalyst while agitating the filtrate, filtering the hydrogenated material and distilling the resulting filtrate to obtain the residual resin.

6. In the manufacture of prepared resin, the method which comprises forming a resinous reaction product by polymerizing a mixture of unsaturated hydrocarbons comprising a fraction of cracked petroleum distillate, reducing the degree of unsaturation of the resin, while avoiding de-.

structive hydrogenation such as to liquefy the resin by hydrogenating the resultant resinous reaoeaeu 7-. In the manufacture of prepared resin, the method which comprises reacting together a mixture of liquid unsaturated hydrocarbons of vary- .ing degrees of unsaturation in the presence of a metallic halide activating agent which hydrolyzes to give an acid reaction to produce an unsatugenation such as to liquefy the resin.

- tion such'as to liquefy the resin.

rated resinous reaction product dissolved in residual liquid hydrocarbons, neutralizing the re.-, action mass, separating undissolved materials from the neutralized mass, reducing the degree of unsaturation of the resin, while avoiding destructive hydrogenation such as to liquefy the resin by hydrogenation in the presence of a hydrogenation catalyst, filtering the hydrogenated material, distilling the resultant filtrate, and introducing into the residue an inert nonaqueous gaseous fluid while heating and agitating the residue.

8. In the manufacture of prepared, resin, the

- method which comprises reducing'gthe degree of unsaturation of the resin by-hydrogenating an unsaturated synthetic resinous reaction product produced by polymerizing a mixture of unsaturated hydrocarbons consisting of a substantial number of the members of the group of hydrocarbons present in a fraction of cracked petroleum distillate, while avoiding destructive hydrogenation such 'as to liquefy the resin.

9. In the manufacture of prepared resin, the

method which comprises passing a stream of hydrogen gas into a solution of an unsaturated polymerized resinous hydrocarbon produced .by polymerization of a cracked petroleum distillate fraction, in the presence of a hydrogenation catalyst and while agitating the solution whereby the degreeof unsaturation is reduced, while avoiding destructive hydrogenation such as to liquefy the resin.

10. A synthetic resin comprising a resinous polymerization product of unsaturated cracked petroleum hydrocarbonsoi' varying degrees of unsaturation and further characterized in that its 12. In the manufacture. of preparedresin, the method which comprises reacting a fraction 0! cracked petroleum distillate in the presence of a metallic halide activating agent which hydrolyzes to give an acid reaction to produce a colored unsaturated resinous polymerization product, and reducing the degree of unsaturation 'of said product by hydrogenation to produce a light yellow, hard resin, while avoiding destructive hydrogenation such as to liquefy the resin 13. A synthetic hydrocarbon resinous polymer obtained byreducing the degree of unsaturation by hydrogenation, of an unsaturated resinous hydrocarbon polymer formed by the polymerization in the presence of a metallic halide activating agent of a cracked petroleum distillate fraction,

while avoiding destructive hydrogenation such as to liquefy the resin.

14. A synthetic hydrocarbon resinous polymer obtained by reducing the degree of unsaturation by hydrogenation, of an unsaturated resinous hydrocarbon polymer formed by the polymerization ot'a cracked petroleum distillate fraction, while avoiding destructive hydrogenation such as to liquefy the resin. I

15. In the manufacture of a resin which is essentially a polymerized unsaturated hydrocarbon, wherein a liquid'mixture composed essentially of "cracked liquid petroleum hydrocarbons which are capable of forming resins under the influence of a polymerizing agent, is polymerized in the presence of a polymerizing agent after which the reacted mixture is treated to separate the polymerizi'ng agent from the polymerized product, the improvement characterized in that the polymerized product is subjected to the action 'of elemental hydrogen and a hydrogenation catalyst under I 'conditionswhereby the color of the product is improved, vwhile avoiding destructive hydrogenation such as to liqliefy theresin. r 16. Inthe mandfactureot prepared resin, tlie ture of liquid unsaturated hydrocarbons of vary ing degrees-oi unsaturation with an acid reacting polymerizing agent, whereby a solution ofresin, dissolved in residual liquid hydrocarbon, is

obtained; neutralizing the reaction mass, separating undissolved. materials from the neutralized mass, and finally reducing the degree of unsaturation of the resin by hydrogenation while avoiding method which-comprises reacting together a mixdestructive hydrogenation, such as would liqueiy the'resin.

cnannas A. moms. wnmammpaauonr. 

